Anthraquinone thioxanthone dicarbazoles



Patented Jan. 17, 1950 UNITED PATENT :ANTHRAQUINGNE THIGXANTHONEDIOABBAZOLES Fritz Max, Easton, "Pa an?! David I. Randall, Phillipsburg,N. :I.,assignors to General Aniline & Film Gorporation, New York, "N.Y.,a corporajtion 6f elaware No Drawing. Application December 5, 1946,Sefiiil N0. 714,148

1'Claim. (Cl. 260316) oxanthone is condensed with c-chlorarithi a-iquinone. By this condensation, theamino group in the 1-position of thethioxanth'one is substituted by an anthraquinone molecule; It-isemphasized, however, in the corresponding United States Patent 999,785,that these-compounds dye cotton in shades ranging from red to grayishblue.

There has been a demand in the art for some time for dyestuffs which arecapable of dyeing textile fibers, particularly vegetable fibers, inpleasing brown shad'es. method is disclosed for producing anthraquinoneacridone dicarbazole dyes by condensing,lfor example, 1.5-diaminoanthr'aquinone with "3l6-dichloranthraquinone 2.1-N-1.2-N benzacridoneand the intermediate with l-chloro-fB-benzoylamino nthraquinone andringclosing the resulting pro not. It was pointed out, however, that thedyes uffs thereby obtainedldye fibersfrom a hydros fite vat in shadeswhich are primarily yellow brown to olive brown.

We have now discovered a class of vat dyes of the anthraquinonethioxanthone dicarbazole series which are capable of dyeingfibers,,particularly vegetable fibers, from a hydrosulfite vat in verypleasing strong shades ranging from black-brownto Currant.

It is accordingly an object of the presentinvention to provide a classof anthraquinone'thioxanthone dicarbazole vat dyes.

It is a further object of the present invention In U. S. P. 2,238,209, a

to provide a class 'of vat dyes capable of rd yeing vegetable fibersirom a hydrosulfit'e viat in: strong pleasing *s'hades ranging fromblack brown ito current.

Other and further important :o'bje'cts wm z b'e come ap arent-as thedescription proceeds.

The newdyestufis'which are contemplated the-present inventionlmay betypifiewbyithe-ziollowing structural formulae:

wherein X and 3? represent hydrogen, "halogen such as chlorine, bromine*and' the like, :aikyrsuch as methyl, ethyl, propyl, butyl -a'n'd Ithe"like, aro matic such as aryl, i.' e., pl'ien-yl,.-n'aphthylantl thelike, aryloxy such a's phe'noxy and theilikegalk-ylaryl such as 0- or-p-methyl pheny1,;p-.ethylphenyl and the like, aroylamino-suchasbenzoyl- 45 aniino, p-mthylbenzoylamino, p-mthoxybenzoylamino and thelike, alkoxy such as methoxy, ethoxy, propoxy and the like, and R, R1,R2, and R3 represent hydrogen, amino, alkyl as above, alkoxy as above,or aromatic as above.

The new compounds are obtained by condensing a 6'-halogen anthraquinonethioxanthone with a 1.5'- or 1.4-diaminoanthraquinone followed byfurther condensation with a l-halogen-anthraquinone. The resultingproduct is then subjected to ring closure for the purpose of forming inthe compound the Z-carbazole rings possessed thereby. Suitable6'-halogen-anthraquinone thioxanthones for the condensation are:

6'-chloroanthraqinone thioxanthone 3.6'-dichloroanthraquinonethioxanthone 32426-trichloroanthraquinone thioxanthone 3-methyl6-chloroanthraquinone thioxanthone 3 methoxy 6'-chloroanthraquinonethioxan thone 3 -phenyl-4 .6 -dichloroanthraquinone thioxanthone 4'methoxy 6'-chloroanthraquinone thioxanthone3'.4'-dimethyl-6'-chloroanthraquinone thioxanthone 3' phenoxy 6'chloroanthraquinon thioxanwent.

for the condensation, the products which are obtained bear the firstformula indicated above. Compounds depicted by the second formula resultwhen 1.4-diamino anthraquinone is employed. The condensation is carriedout by heating the various components to a temperature ranging fromabout 190 to 250 C. in the presence of an acid acceptor such as sodaash, sodium acetate, potassium carbonate and the like and copper or asalt of copper such as copper acetate and the like.

The ring closure is effected by heating the intermediate formed by thecondensation reactions to a temperature of about to 125 C. in thepresence of an acid condensing agent. The acid condensing agent may bean acid such as concentrated sulfuric acid, chlorsulfonic acid or thelike, but preferably is an acid-reacting metal chloride employed with anon-basic organic sol- Suitable metal chlorides are: aluminum chloride,ferric chloride and the like. The nonbasic organic solvents may be:nitrobenzene, nitrotoluene, dinitrobenzene, tetrachlorethane,chlorbenzene and the like.

The anthraquinone thioxanthone may be formed by reacting a l-halogen ora l-nitro anthraquinone-2-carboxylic acid with a phenyl mercaptanbearing the desired substituents in the 2- and 3-positions(corresponding to the 3'- and 4'-positions of the final product) and ahalogen atom, preferably a chlorine atom, in the 5-position(corresponding to the 6'-position in the final product). The method ofproducing these compounds is specifically described in German Patent243,750.

The manner in which the reaction proceeds when utilizing for example3'.6-chlor anthraquinone thioxanthone, 1.5-diamino anthraquinone and1-chlor-5-benzoylamino anthraquinone is represented by the followingequations:

1- .chlor-5-methyl anthraquinone 3 1 elder-fl.5-dibenzoylaminoanthraquinone 1-chlor-4-phenyl anthraquinone l-chlor-4-methoxyanthraquinone l-ohlor-5-phenoxy anthraquinone and the like. 7

Where a LS-diamino anthraquinone is utilized By suitable treatment ofthe intermediate indicated above, ring closure takes place along thedotted lines to form the desired end products.

The following are examples of compounds embraced by the above formulaeand contemplated by the present invention. For the sake of brevity thenomenclature used indicates the particular substituents in the formulaenoted.

3. The compound is the'same as that of Formula '1 excepting that the3-position is unsubstituted.

4. The compound is the same as that of Formula 1 excepting that the 61position is unsubstituted. H

5. The compound is the same as that of F01"- mula 1 excepting that the 3and 61 positions are unsubstituted.

6. The compound is the same as that of Formula 1 excepting that the3'-position is substituted by methyl.

7. The compound is the same as that of Formula 1 excepting that the 3and 4-positions are substituted by chlorine.

8. The compound is the same as Formula 2 excepting that the 4-positionis substituted by phenyl.

9. The compound is the same as that of Formula 1 excepting that the61-position is substituted by p-methyl-benzoylamino.

10. The compound is the sameas thatof Formula 2 excepting that the31-pos itinis substituted by methyl.

11. The compound is the same as that of Formula 1 excepting that the 3and 4-positions are substituted by ethyl and the 61-p0sition isunsubstituted.

12. Thecompound is thesame as that of Formula 1 excepting that the3-position is substituted by methoxy.

13. The compound is the same as that of Formula 2 excepting that the3-p0sition is substituted by phenoxy.

14. The compound is the-same as that of Formula 1 excepting that the4='-position is substituted by ethoxy and the 61position is substitutedby ethyl.

15. The compound is the'same as that of Formula 1 except that the3'-position is unsubstituted and the 61 position is substitutedbyiphenyl.

16. The compound is the same as that of Formula 2 excepting that the 31"position is substituted by phenoxy.

17. The compound is the same as that of F'ormula 1 excepting that the3-position is substituted by pnopyl and the 61-position is substitutedby ethoxy.

18. The compound is the same as that of Formula 1 excepting that the31'-positi0n is substituted by methyl.

19. The compound is the same as 'that'of Formula 1 excepting thatthem-position is substituted by p-methyl-benzoylamino.

20. NHCOCeHa ITIHC ODEH;

22. The compound is the same as that of Formula 20 excepting that the 3'and 4'-positi'o'ns are substituted by chlorine.

23. The compound is the same as'that of For-:

mula 20 excepting that the 31 and Sf-positions are substituted bybenzoylamino.

24. The compound is the same as that of Formula 21 excepting that the4'-position is substituted by methoxy.

25. The compound is the same as that of Formula 20 excepting that the3'-position is substituted by methyl.

Example I A mixture of 13.7 parts of anthraquinone-2,1- (S)-1,2' (S)3',6' dichlorothioxanthone, 7.6 parts of 1,5-diamino anthraquinone, 5.0parts of soda ash, 1.0 part of copper acetate and 360 parts ofnitrobenzene are heated for 4 hours at 205 G. Then 12.1 parts ofl-chloro 5 -benzoylamino anthraquinone are added and the mixture isstirred for hours at 205 C. After cooling to 70 0., the condensationproduct is isolated by filtration. The precipitate is washedsuccessively with ethanol, dilute hydrochloric acid and water. Theanthrimide dyes cotton violet shades from a violet vat.

For carbazolation 24.6 parts of the above anthrimide are dissolved at 60C. in a solution of 60.0 parts of aluminum chloride in 240 cc. ofnitrobenzene and stirred while heating at 90 C. for 1 hour. The colorchanges from green to greenish blue during the heating period. It isthen poured into 1500 parts of ice water and 50 parts of 36%hydrochloric acid. The nitrobenzene is removed by steam distillation andthe crude dyestufl filtered. Cotton is dyed by this product from aviolet vat in strong neutral brown shades of very good fastnessproperties.

Example II A mixture of 27.4 parts of anthraquinone-2,1- (S)-1,2'-(S).3,6' dichlorothioxanthone, 15.2 parts of 1,5-diamino anthraquinone,10.0 parts of soda ash, 2.0 parts of copper acetate and 730 parts ofnitrobenzene are stirred at 205-210 C. for 4 hours. Then 12.1 parts of1-chloro-4-benzaminoanthraquinone are added and stirring at the abovetemperature is continued for 15 hours.

The anthrimide is worked up as in Example I. It dyes cotton violet-grayshades from a violet vat.

For carbazolation 29.2 parts of the anthrimide are added to a stirredsolution of 60.0 parts of aluminum chloride in 240 parts ofnitrobenzene. The temperature is raised to 90 C. and held for 45minutes. At the end of the heating period the color has changed fromgreen to olive brown. The dyestufi is worked up as in Example I. Thefinished dyestuif dyes cotton in powerful chocolate-brown shades andpossesses excellent fastness properties.

Example III A mixture of 13.7 parts of anthraquinone-2.l- (S) 1.2 (S)3.6'-dichloro thioxanthone, 7.6 parts of 1.4-diamino anthraquinone, 5parts of soda ash, 1 part of copper acetate, 350 parts of nitrobenzene,are stirred at 205 C. for 4 hours. Then 12.1 parts of1-chloro-5-benzoylamino an- 8 thraquinone are added and the mixture isstirred for 15 hours at 205 C. The anthrimide is worked up as in ExampleI.

The carbazolation is run as in Example I. The finished dyestufi dyescotton brownish violet shades from a violet vat, the dyeings possessingvery good fastness properties.

Example IV The procedure is the same as in Example 11 excepting that1.5-diamino anthraquinone is replaced by 1.4-diamino anthraquinone.

Example V The procedure is the same as in Example I excepting that theanthraquinone-3'.6-dichloro thioxanthone is replaced byanthraquinone-2.1- (S) 1.2' (S) 3 phencxy 6' chloro thioxanthone.

Various modifications of the invention will occur to persons skilled inthe art. For instance, instead of preparing the dyestufis in the mannerindicated, they might also be prepared by first condensing a5.5'-diamino-1.1-dianthrimide carbazole with an anthraquinone-2.l-(S)-1'.2-(S)- 6'-chloro thioxanthone and carbazolizing the resultinganthrimide. If the compounds are to contain a benzoylamino group, thesame may be introduced by benzoylating the free amino group. Wetherefore do not intend to be limited in the patent granted except asnecessitated by the prior art and the appended claim.

We claim:

The compound of the formula:

fl) NHCOCcH;

which dyes cotton from a hydrosulfite vat in brownish violet shades ofexcellent fastness properties.

FRITZ MAX. DAVID I. RANDALL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,212,965 Wieners et a1 Aug. 27,1940 2,238,209 Bauer et a1. Apr. 15, 1941 OTHER REFERENCES Fierz-David:Kunstliche Organische Farbstoffe, Julius Springer, Berlin (1926), vol.3, pages 603. 604.

